Hydrocarbon Oxidation Methods for Synthesis

烃氧化合成方法

• 批准号: 7679383
• 负责人: Maria White
• 金额: $ 28.6万
• 依托单位: UNIVERSITY OF ILLINOIS AT URBANA-CHAMPAIGN
• 依托单位国家: 美国
• 财政年份: 2006
• 资助国家: 美国
• 起止时间: 2006-09-26 至 2011-08-31
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/7679383
• 关键词: Acetates; Acids; Alkenes; Amination; Amines; Amino Alcohols; Applications Grants; Benzoquinones; Carbamates; Chemicals; Chromium; Complex; Data; Development; Esters; Goals; Grant; Hexoses; Hydrocarbons; Isotopes; Kinetics; Ligands; Macrocyclic Lactams; Macrolides; Methodology; Methods; Modeling; Modification; Nature; Nitrogen; Oxygen; Palladium; Pharmaceutical Preparations; Phosphines; Phosphites; Process; Property; Reaction; Reaction Time; Reagent; Research; Research Personnel; Route; Scheme; Solid; Staging; Sulfoxide; System; base; catalyst; chemical synthesis; design; functional group; improved; oxidation; programs; salen; tool

DESCRIPTION (provided by applicant): The primary focus of this proposal is the discovery and development of highly selective, catalytic allylic C-H functionalization reactions that can be broadly applied to synthesis. Using these reactions to develop strategies for effecting highly efficient syntheses of molecules with valuable properties is one of our ultimate objectives. Another key objective is the mechanistic study of such systems in order to elucidate new fundamental principles of catalyst design and chemical reactivity. We have recently discovered a new class of sulfoxide-based palladium allylic C-H oxidation catalysts that provide access to either linear (E)-allylic acetates or branched allylic acetates from a wide variety of terminal olefin substrates. The distinctive features of these allylic C-H oxidation systems is that they require no heteroatom directing functional group on the substrate to achieve high reactivity and regioselectivity and are extraordinarily functional group tolerant. This revised grant application details our plans to fully optimize, based upon preliminary findings, these two reactions for use in fine chemical synthesis. Towards this goal, we have new preliminary data that: 1. identifies conditions to effect catalytic enantioselective branched allylic oxidation, 2. supports the claim that the allylic C-H macrolactonization method we propose to develop will have broad scope, 3. suggests that other nucleophiles will be competent for allylic C-H functionalization. On the basis of these results, we propose the following: 1. detailed mechanistic studies to determine the nature of reactive intermediates in the two allylic oxidation systems and the effects of sulfoxide and BQ on their formation and reactivity; 2. development of the branched allylic oxidation reaction into an enantioselective process and macrolactonization method for widespread use in synthesis, 3. optimization and use of the linear allylic oxidation reaction to effect a highly streamlined route to the hexoses, 4. exploration of the Pd/sulfoxide reaction manifolds for effecting a broad range of allylic C-H functionalization reactions. The discovery and development of mild and selective C-H functionalization methods, like the ones described in this proposal, stands to impact significantly on both the rate and expense in which new drugs are discovered and manufactured.

描述（由申请人提供）：本提案的主要重点是发现和开发可广泛应用于合成的高选择性，催化的烯丙基C-H功能化反应。利用这些反应来开发高效合成具有有价值性质的分子的策略是我们的最终目标之一。另一个关键目标是对这些系统进行机理研究，以阐明催化剂设计和化学反应性的新基本原则。